Design and Synthesis of Calixarene Scaffolds Bearing Hydrogen Bond Motifs Farzad Fani-Pakdel and Jason R. Telford Department of Chemistry, University of Iowa Iowa City, IA

Calixarenes: Calixarenes are macrocycles that are made from phenol or P-tert-butylphenol Calixarenes and its derivatives can be used to complex a range of cations, anions and neutral molecules. Calix[4]areneCalix[8]areneCalix[6]arene

Synthesis of Calix[4] and [8] Derivatives: Calix[8] Calix[4]

NMR of Calix[8] Derivative Derivative Calix[8] 14 Carbons are present in C-13 NMR Of derivative

Calix[4] derivative: NMR and IR Calix[4] Calix[4] derivative

Calix[8] derivative a hydrogen bond acceptor Structure and space filling model for calix[8] derivative.

Crystal Structure for Calix[4] Derivative  Hydrogen atoms are not shown.  There is a cavity that can be both hydrogen bond donor and acceptor  It can also bind metals through O / N in a Td cavity.

Comparing 1:1 with 1:2 complex of calix[4]derivative: fluoride. Using Hyper NMR 1:1 1:2

Acknowledgements:  Department of Chemistry, University of Iowa  Carver Scientific Research Initiative  Dr D. J. Burton  Dale Swenson  Telford Research Group

Cu(NH 3 ) 4 2+ and Cu(Arg)Cl 2 As guests for Calix[8] derivative Using Spartan-pro software

Future Work Now that we have made some supramolecular hosts we are systematically testing organic ligands that match our super-molecule in size, hydrogen bonding and other intermolecular interactions. We will also investigate the metal complexes of such compounds in order to evaluate outer sphere metal-complex recognition. In order to study these interactions, NMR, UV-Vis, fluorescence, mass spectroscopy and finally crystal structures will be used.

1 2 Calix[4]arene derivatives

Calix[8]arene derivatives

TBDMSCl Pyridine P(Ph) 3, Br 2 1. NaH / THF 2. MeI DMF Figure 3.1.Reaction shim for making compounds 9-11  -cyclodextrin derivatives

1. NaH / THF 2. Ph-CH 2 Br 12 11

Spartan-pro side view of compound 12

Side view, space filling